Salts of reaction products of epoxidized acyl radical containing compounds and polyamino compounds



-, 2,953,585 1 =Passed;sepeaoqssn;

SALTS OF REACTION PRODUCTS OF EPOXIDIZED ACYL RADICAL CONTAININGCOMPOUNDS AND POLYAMINO COMPOUNDS Melvin De Groote and Jen-Pu Chen g,University City, Mo., assignors to Petrolite Corporation, Wilmington,Del., a corporation of Delaware 1 No Drawing. Filed Apr. 13, 1956, sr.No. 577,955

7 Claims. (11. 260-4045 The present invention is concerned with the-saltform of the reaction products of certain acyl radical containingepoxidized compounds, and most conveniently epoxidized glycerides andepoxidized monohydric alcohol esters, and polynitrogenous compounds,i.e., compounds having 2 or more nitrogen atoms and preferably basicamino compounds, in which there is at least one and in many instances 2or more basic nitrogen atoms. salt form may include partial salts, i.e.,compoundsoin which there is an ester or an acid radical or both, but inany event at least one cation. V

The products herein described may be employed for a large variety ofpurposes and include not only the complete salts but acid salts andester salts as well. Furthermore, these salts can be used asintermediates for conversion into other products.

- The products also may be used as intermediates for further reaction. Y1

The initial presentation of the present invention is best adapted to aconsideration of such instances where an ester of a monohydric alcoholis involved rather than the ester of a diol, or triol such as aglyceride. .If an epoxidized fatty acid ester derived from a low molalalcohol,

such as a methyl, ethyl, propyl or butyl ester, is.,subjected toreaction with a polyamine the resultant product may be indicated thus:o. w

in which the fatty acid acyl radical prior to expoxidation is the acylradical of the fatty acid in which R and R are the conventionalhydrocarbon radicals of unsaturated fatty acids having not overv 22carbon atoms; and in which R is the monovalent radical of a polyaminehaving at least one basic nitrogen atom, said radical being formed bythe removal of a hydrogen atom from the polyamine during linkage withthe carbon atom, and R" is a radical derived from a low molal alcohol aspreviously described.

If, on the other hand, 2 moles of the epoxidized ester are combined with1 mole of a polyamine, such as triethylene tetramine, then the productderived is as follows:

in which the various characters have their prior signifivalent radicalderived from the precursory polyamine.

with causticsod'a or caustic potash, one thenobtains products such asthe following i CB:s--1'i.t--[ (1J J-RaCOO r H--OH' in whichthe cationwould be sodium or'potassium.i If, on the other hand, one obtained thefree=a id;;=a t;,- least in the instance of the secondformula, one couldobtain an acid salt. Toobtain thejester salt one would: react 2 moles ofthe epoxidized monohydricalcohol esterrv with one mole of polyamine andthen add enough of-the caustic soda or'caustic potash to saponifyone'esterv radi calonly. i e After the sodiumsalt or potassium salt hasbeen Ob -.7 tained, the product can be subjected to double decom.-;;position with a soluble salt of barium, calcium, magne-; sium'strontium, aluminum, iron; copper or the-like, and. the metallic salt soobtained subjected to dehydration; to yield the anhydrous salt.-" Theinvention is; thus diff rected to a member selected from theclassof'salts and acid salts of the structure 'f and: 5

in which R and R are'the conventional hydrocarbon radicals ofunsaturated fatty acids".composed only of carbon, hydrogen and oxygenatoms'having not over 22 carbon atoms and each containing at least 3carbon atoms;

in which R is the radical of a polyamine composedonly of-carbon,hydrogen, nitrogen and oxygen atoms, having up to20 carbon atoms, andhaving at least'one basic" nitrogen atom, said radical being formed bythe'remova'l. of a hydrogen atom from an amino nitrogen. atom of thepolyamine during rupture of the oxirane ring and linkage; oftheaminonitrogen atom with a carbon atom of the oxirane ring, and R isthe radical \of a polyamine coma, posed only of carbon, hydrogen,nitrogen and oxygen atoms, having not over 20 carbon atoms'andhavinga't, least one basic nitrogen atom, said radical being formed; bythe removal of one hydrogen atom from each oftwq. separate aminonitrogen'atoms of the polyamine during rupture of the oxirane rings andlinkage of theaminq nitrogen atoms with the carbon atomsiof the 'oxiranerings; and n is a whole number not over 3 andin which'Z is selected fromthe group consisting of group Ia, Ib, IIa-, Hb and IHa metal ions, andthe cation is selected from the group consisting of Z, hydrogen, andlower alkanol radi- 1 cals and must include at least one equivalent of Zper If products of the kind described above are saponified anron. a Forpurpose of convenience what is said hereinatten will be divided into sixparts: 5 Part 1 is concerned with derivatives'obtainedby the epoxidationof fatty acids or-fatty -acid compounds Torfatty acid salts which areparticularly suitable for reaction with a polyamine;

Part 2 is concerned with polyarnino compounds particularly suitable forreaction with the epoxidized compounds. described in Part 1;

Part 3 is concerned with the reaction involving the two classes ofreactants above, i.e., those described in Part 1 and those described inPart 2, and is divided into three sections. Section 1 is concerned withthe reaction between the polyamines and epoxidized monohydric alcoholesters, Section 2 is concerned with similar reactions in whichepoxidized glycerides or the like replace the monohydric alcohol esters,and Section 3 is concerned with the reactions in which the epoxidizedfatty acid salt is employedg' Part 4 is concerned with thesaponification of the ester type of reaction product of Part 3 so as toconvert the amino radical containing reactant into a free acid orpartial ester which, in turn, can be converted by neutralizat-ion orsaponification into the salt of an alkali metal such as sodium orpotassium. It is to be noted that these salts, including partial salts,along with the products obtained in the manner described in Section 3 ofPart 3, preceding, typify the products of the present invention;

Part 5 is concerned with the preparation of the barium, aluminum orcalcium salts, particularly by use of a solution of the sodium orpotassium salts; and

Part 6 is concerned with various uses for the products described in Part5, preceding.

PART 1 Reference is made to our three co-pending applications, SerialNo. 532,121 filed September 1, 1955, Serial No. 548,748 filed November23, 1955, and Serial No. 548,749 filed November 23, 1955.

The epoxidation of ethylenic compounds and particularly esters ofunsaturated fatty acids, unsaturated aliphatic alcohols, and theunsaturated fatty acids themselves, is well known. For instance, it hasbeen described in the following patents:

U .S. Patents Nos.

Additionally epoxidation procedures have been described in the tradeliterature of organizations which supply one or more reactants employedin the procedure. For instance, see Bulletin P63-355 entitled HydrogenPeroxide-Resin Technique for the Preparation of Peracetie Acid, E. I. duPont de Nemours & Company; Bulletin P61-454 entitled HydrogenPeroxide-Resin Technique for Epoxidation of Unsaturated Fats, Oils, andDerivatives, E. I. du Pont de Nemours & Company; and booklet entitledHydrogen Peroxide issued by Buffalo Electra-Chemical Company, Inc. Seealso Chemical Week, August 21, 1945, page 100; and Chemical Week,December 25, 1954, page 32.

Fatty acids and fatty acid derivatives which may be subjected toepoxidation by conventional procedures are illustrated by the following:

In the above formulas R and R represent monovalent and divalenthydrocarbon radicals having at least 3 carbon atoms. R is a divalentradical.

Stated another way, it is preferable that the ethylene linkage which issubjected to epoxidation is at least 2 car- In the last formula n is asmall whole number varying from 2 to 6 for example, which corresponds tothe valency of the multivalent radical R".

Needless to say if one prepares esters of dihydric ai cohols such asethyleneglycol, propyleneglycol, and diethyleneglycol, one can producemolecules having 1.75 to 4 oxirane rings per ester molecule. Similarly,t-rihydric esters can be obtained from trihydric alcohols, such astrimethylol ethane, trimethylol propane, etc. The number of oxiranerings would correspond to those of an ordinary glyceride. If oneprepared an ester from a tetrahydric alcohol such as dig-lycerol,pentaerythritol, oxyethylated pentaerythritol, etc., the number ofoxirane rings could vary from 3.3 to 8. In the case of a complete esterof a heXitol, such as sorbitol or oxyethylated sorbitol, the number ofoxirane rings could vary from 5 to 12. However, for practical purposesthe most economical derivatives in many instances are those described inaforementioned U.S. Patent No. 2,556,145.

If one employs an epoxidized glyceride as, for example, epoxidizedsoybean oil, there is a possibility that the number of epoxide groupsare less than one per acyl radical. In other words the value may varyfrom 2.1 to 2.7 oxirane rings per glyceride radical which may mean thereis present at least in part of the glyceride a non-epokidized acylradical. If such a product is then reacted with a polyamine and thenconverted into a salt, such as the sodium or potassium salt, obviouslythe percentage of active iiiaterial is less than if one were certain tohave atleast one oxirane ring in each acyl radical.

From a practical standpoint it would appear simpler to use an epoxidizedfatty acid prepared in the manner pre-' viously described. In many waysit is difficult to prepare an epoxidized fatty acid on a large scale andthe product is not particularly stable. One can obtain, however, sodiumepoiiystearate or potassium epoxystearate and such products areparticularly suitable as reaction products and have the added advantagethat neutralization with caustic soda is not required. However, in manyinstances the most desirable material for epoxidation is the fatty acidester of a monohydric alcohol such as methyl al cohol, ethyl alcohol,propyl alcohol, or butyl alcohol. Such product can be epoxidized so asto have approximately one oxirane ring per acyl radical and avoids thepresence of a non-epoxidized reactant as sometimes happens in the caseof the glyceride.

As is well known the amides and the amines of fatty acids can besubjected to epoxidation and the resultant product employed as a fattyacid equivalent within the scope of the present invention. For instance,the fatty acid amides, particularly amides of 9,10-epoxystearic acid,are described in U.S. Patent No. 2,567,237, dat'ed September 11, 1941,to Scanlan, et a1. We have prepared similar amides from diamines inwhich there were 2 fatty acid groups and 2 amino groups.

The vegetable oils which when epoxidized may be used in practicing thepresent invention are those glycerides of saturated and unsaturatedacids which have a degree of unsaturation represented by an iodine valueof from to 205 and in which the fatty acids neither are hydroxylated norpossess conjugated unsaturation. The semi-drying vegetable oils, whichare primarily glycerides of oleic and linoleic acids, are preferred.Among those oils which may be used are epoxidized peanut, rapeseed,cottonseed, corn, tobacco seed, cucurbit, sunflower, safliower;poppyseed, linseed, perilla, and soybean oils. Of these epoxidized;oil-s, soybean oil is particularly efficient. Theoretically, each carbonto carbon double bond of the 8 original vegetable oil can be convertedtoepoxy group. In practical operation this will seldom, if ever, beattained but it is desirable that highly epoxidized Oils be used so thatmaximum stability be efiected. It is recommended that there be usedepoxidized oils containing anaverage of from 2 to 6 epoxy groups permolecule.

If the fatty acid group has some other functional group present,diificulty may be involved in obtaining optimum yields for some reasonthat is not entirely clear. This would apply, for example, to castoroil, and ricinoleic acid esters. On the other hand, if castor oil isreacted with a low molal acid such as acetic acid, propionic acid, orthe like, then these difliculties appear to be eliminated. There alsoappears to be difiiculty in obtaining suitableyields in the case ofconjugated unsaturation. In some instances where the unsaturation is'notconjugated there is indication that there may be a shift during reactionto produce conjugation. In other Words, in the epoxidation of the fiattyacid or fatty acid ester or the like, if the fatty,

acid is polyethylenic it is very important that the ethylenic radicalsbe non-conjugated. The fatty. acids themselves may contain 8 to 22carbon atoms.- The best exampleof. the monoethylenic acid is, of course,oleic, acid and perhaps erucic acid. Both are readily available asglycerides. As to the polyethylenic acids, particular attention is di--rected to linoleic. As to an example of an acid having 3 ethyleniclinkages attention is directed to linolenic. These acids, of course, areavailable in the formvof glycerides, particularly mixed glycerides.Other polyethylen ic acids are obtained from oils of aquatic origin,

PART 2 The polyamines which may be employed as' reactants in which R" ishydrogen, alkyl, cycloalkyl, aryl, or aralkyl aminf latter is ofparticular interest becausethe product is commei'cially available'inlight of itsfusej in the manufacture bf synthetic fibre. If desired, onecan prepare a variety of reactants having two or more amino groups andat least one hydroxyl group. One may use modificationsof procedures orthe procedures themselves as described in US. Patents Nos. 2,046,720dated July 7,, 1936, to Bottoms; 2,048,990 dated July 28, 1 936, toBritton et al.; 2,447,821 dated August 24, 1948, to Sankusiand'1,985,885 dated January 1, 1935, to Bottoms. Examples include thefollowing:

NHzCHnCHOHCHz ,l

H o ,7 Y --H HqN-OH0H -CH;OGH CH -NH H H Other suitable amines areexemplified by ethylenebisoxypropylamine.

omo CH2CH2CH2NH2 rnoomorncnmm and R is a divalent radical such as C H-CH;,

H pylamine with 1, -2, 3 or 4 moles of ethylene oxide, pro- H L L pyleneoxide, butylene oxide, or the like.

CHZ CH3 CH3 (lJHfl 5 Other compounds including those having cyclicstructures include piperazine, and the corresponding deriva-- CH CH- OHtives obtained by treating piperazine with alkylene oxides. CH5 CH3 CH3The same applies to substituted piperazine such as the Stated anotherway, the polyamines haye at least one primary amino group separated fromanother primary" or secondary amino group by 2 to 4 carbon atoms.Examples of suitable amines include:

Ethylenediamine Diethylenetriamine TriethylenetetramineTetraethylenepentamine Propylenediamine Dipropylenetn'amineTripropylenetetramine Butylenediamine AminoethylpropylenediamineAminoethylbutylenediamine Other polyamines in which the nitrogen atomsare separated by a carbon atom chain having 4 .or more carbon atomsinclude the following: Tetramethylenediamine, a V

(3) Similarly, a comparable diamine, presumably obpentamethylenediamine,and especially hexamethylenediand' derivatives obtained by treatingethylenebisoxypro- 2,5-dimethylpiperazine. --As-tomono-substituteddialkanol piperazine see US. Patent No. 2,421,707, dated June 3, 1947,to Malkemus.

Another example of polyamine which may be employed as'a'reactant is thatdescribed as Duomeens."

5 TABLE I IDuomeen is a trademark designation for certain diamines madeby Armour Chemical Division, Armour & Company, Chicago, Illinois. TheDuomeens have the f llowing general formula:

R is an .alkyl group derived from a fatty acid or from (l) Duomeen 12R=Coconut oil fatty acid 7 tained from Rosin Amine D and acrylonitrile,is obtainable from Hercules Powder Company, Wilmington, Delaware. Thecomposition of Rosin Amine D is as follows:

It is to be noted that all the above examples show high molal groups,i.e., 8 carbon atoms or more. The

amyl, hexyl groups, or the like, appear instead of octyl,

Gib/CHINE! 5 decyl, etc., are equally satisfactory.

PART 3 ction 1 CH: Se (1H The present section is concerned with thereaction be- CH; tween the po'l-yamine's and epoxidized monohydnc al-Polyamines from monoamines and cyclic imines, such 301101 estersp I asethylene imina For purpose of brevity we are going to limit the ex- Hamples to esters which are available commercially or can be obtainedfrom suppliers of epoxidi'zed products. Noam ethylenedmmme These estersare epoxybutyl stearate, isobutylepoxy- H acetoxy stearate, andmethylepoxy soyate. I OuHrv-N-CHzCHz-NH: As previously pointed out thereaction involvingthe N-tetradecyl ethylenedlamine reactant containingthe oxirane ring and polyamine is H essentially a variety ofoxyalkylation. For this reason CwHarN-Cm-CHrN the reactions are soconducted The procedure is simpler N-hexadecylethylenediamine than isthe case when ethylene oxide or propylene oxide 11 H C H g C H NH isused for the reason that the reactants are non-volatile 2 l as a ruleand thus one does not have to use an autoclave N'dodecyltriethylenetetramme ,or similar equipment. Furthermore, many of thereact- H C12H N c!H NH2 ants employed are bas c in character and thus tothe e rtent Ndodec 1 r0 lenediamme required act as their owncatalyst. Ashas been pointed y Dy out elsewhere catalysts can be added, particularlyalkaline catalysts such as sodium methylate, caustic soda, causticNdecyl butylenedmmine potash, etc. In a general way, the procedureemployed 0) polyammes containing tertiary amino groups: in preparing theproducts is the same and the only prc- Cam caution taken as a rule1stoavo1d temperatures above E that required to rupture the oxirane ringfor the reason GIIHHN-OIHPN'WH that side reactions or secondaryreactlons may take place.

TABLE 1 Oxirane Oxyalkyla- Ex. Ring 0011- Amt, tion Sus- Amt Temp, Time,Product of No. taining; Regms. ceptible gms; 0. Hrs. Reaction actant:Reactant 1a..-. Epoxybutyl 184 Aminoethyl 155 110 3 D lgbrn. vise.

stearate. Stearannde 150 0.5 liq.sol. inalcohol and xylene. 2a..-----..do 150 Hydrsztne. 13.7 110 3 White creamy emul. with 5% 11,0 111hydrazine. Sol. in hot xylene and 1:20- propanol. Crysstalltne in coldxyl. and. lsopropanel. 30.... .....do....... 175 Ethylene 35 110 3 Brn.llq. sol. in

dlamlne xylene and im- Drop. 40.... .-..-.do 175 Diethylene 49 110 3Brn. liq., sol. in

triamlne xyl. and lsopr'opanel. do 150 'Iriethylene 59.5 110 3 Brn.l1q., sol. in

tetramine. xyl. and lsopro PBJJO an do 176 Tetraethyl- 3. Brn.llq:sol.ln

ene peuxyl. lsoprotarnlne. panel and water. 7m. .---.do 150 Propylene30.2 110 3 Brn. liq; sohln dlamine. xyl. isopro! panel and water. 8a.-.--..--do 150 Propylene 36.2 110 3 Brn. liq. sol tn trismlne. xyl. andlsopropanol do 160 Duomeen B. 164.0 3 Lt brn.semtsolid sol. in xyl. andisopropanol 10:; do Hydroxy- 42.8 115 3 Lt.brn.llq. sol.

ethyl 1n xyl. and

ethylene lsopropanel. dlamlne.

Duomeen S 18 an ammo propyl alkylamme,

RNHC H NH, derived from soyafatty acid. It is a product of ArmourChemical Company.

TABLE 2 Oxirane Oxyalkyia- Ex. Ring Con- Amt., tion Sus- Amt Temp.,Time, Product of No. taim'ng Regms. ceptible gms. O. Hrs. Reactionactant Roaotant 11a... Isobutyl- 241 1,6 hexane- 30.3 115 4 Dk.bm.liq-1- epoxydlamine. in xyl. and aeetoxy alcohol. stearete. 12a--- do 241 do60. 115 3 Brn. liq. sol. in

xyl. and Y alcohol. 13a.. do. 241 m-phenylcne 44.0 120 2 Black vise.liq.

dlamine. 160 2 sol. ln xyl. and

alcohol. 14a-.. Methyl 150 Ethylene 38 120 2 Brn. vis. liq. sol.

Epoxydlamine 150 0. 5 in xylene and soyate. (78%). lsopropanol. 15a----do 150 Propylene 37 .120 1.5 Drk. bm. vis.

dlemine. 150 0. 5 liq. sol. in xyl.

and alcohol ml! in 150 M-phenyl- 54 120 2 Drk. brn. very one dia- 165 2vis. liq. sol. in mine. 1 xyl. and

' 7 alcohol. 17': do 160 Hydrazine 17 110 3 White creamy liq. sol. inhot xyl. and isopropanol. 180 do 150 Hydroxy- 53 3 Yel. vis. liq. xyl.

ethyl 130 0. 5 and isoproethylene V panol soluble. diamine. 190... do300 Propylene 37 2 Brown vis. liq. dlamine. 150 0. 5 sol. in xylene andalcohol. 2042.... do 300 Ethylene 38 120 3 Brown, very diamine 150 0. 5visc. liq. sol. in (78%). xylene and 1- alcohol.

Methyl Expoxysoyate-Expoxidlzedj methyl ester of soybean iatty ecid.

PART 3 Section 2 The present section is devoted to derivatives obtainedby means of epoxidized glyoerides, such as cpoxidized soybean 011.

TABLE 3 Oxirane Oxyalkylaj V Ex. Ring Oon- Amt, tion Sus- Amt, TempTime, Product of No. taming Regms. ceptlble glue. 0. Hrs. Reactionactant Beactant 1b..-- Expoxldized 150 Diethylene 57 105 3 Amber viscoussoybean triamine. 130 0. 5 liq. sol. oil. xylene and I isopropanoL20...... do Amine 333... 67.6 105 3 Orange viscous 0. 5 liq. sol. in

xylene and isopropanol. 35.... ...do Hydroxy- 55.4 105 3 Yel. vise. liq.

ethyl 130 v 0.5 sol. in xylene v ethylene and isoprodiamine. panol. 7 p40.... d0 150 Diemino- 37 105 3 Light brown propane. 130 0. 5 vise. liq.sol.

' in xylene and r isopropanolh V 50 do 150 3,3 Imino 65. 5 105 3 Darkred vise.

bispropyl- 150 0. 5 llq. sol. in amino. xylene and alcohol. 65.... do150 Betahy- 38 105 *3 White waxy droxy- 130 0. 5 solid sol. in ethyl hotxylene and hydrazine. hot isopropanel. 75.... ...--do 150 N,N-dlethyl 58115 3 Dark amber 1 ethylene V visc. liq. diamine. xylene and 150 0. 5alcohol soluble.

TABLE 4 Qxirane Oxyalkyla- Ex. R ng 0011- Amt., tion-Sus- Amt, Temp,Time, Product of N o. taming Regms. ceptible gms. O. Hrs. Reactionactant Reactant 8b..-- Expoxidized 162 Propylene 26. 7 110 3 Drk. brn.semitriacetyltriamine. solid, sol. in ated xyl. and isocastor 011.propanol. 9b-..- do 162 m-phenylene 32. 4 120 2 E ViS- e idiamine. 160 2solid, sol. in xyl. and ale.

10!)... do 189 Hydrazine. 12 110 3 White creamy semi-solid, sol. in hotxyl. and hot lsopropanel.

110... .do 135 Duomeen S. 100 130 3 Lt. brn. semisolid, sol. in xyl. andisoprop.

12b.-. do 162 N-phenyl-Z- 49 130 3 Brn. vise. liq

methyl-1, sol. in xyl. and 2-propane cohol. diamine.

Amine 333 is a product of Mathieson Chemical Corporation. It is composedof diethylene triamine, triethylene tetramine and tetraethylenepentarnine in equal weight proportions.

PART 3 Example 1c A 500 ml. 3-necked flash was fitted with a refluxcondenser, a thermometer and an elficient sealed stirrer. In

the flask were placed 25.8.grams of diethylene triamine and 250 grams ofmethanol. When the triamine and' methanol had been completely mixed,88.8 grams of powdered sodium epoxystearate were added and vigorousstirring was applied. The mixture remained a white suspension while itstemperature rose spontaneously from. 25 to 29 C. As soon as thetemperature ceased to rise, heat was applied gradually to bring themixture to a gentle reflux at 70 C. The suspension became homogeneous:at the reflux temperature. After the heating had been continued for 3hours, the reaction was complete and the product was poured into a 800cc. beaker to cool into a white solid gel. The solid gel was insolublein the methanol solventI It was ground with a stirring rod, filtered bysuction, washed with isopropanol and dried under vacuum. The driedproduct was a white solid powder, soluble in water and hot-"methanol,insoluble in xylene, isopropanol and dioxane.

TABLE 5 Oxirane ring- Amt., Polyamlno Amt., Solvent Temp; Time, Productof Ex. N 0. containing gms. Reactant gins. Meth- 0. hrs. ReactionReactant anol, gms. 1c Sodium epoxy 88.8 Dicthyle'ne 25.8 250, j 71 3White solid sol. in stearate. triamine'. i .wtr. and hot methanol,insol. in benzene and cold ale.

2c do 88. 8 Tetraethylene 47. 2 260 70 8 Yel. white solid.

pentamine S01. in wtr. and

hot methanol; insol. in bezene and cold meth.

3c do 88.8 Tetraethylene 23.6 250 p 71 4 White'soitsolld. pentamine.801. in wtr. sltly.

sol. in benzene. Sol in hot methanol. 4c do 88.8 Duomeen S-.- 82 250 713 Yel. waxy solid.

sol. in isopropanol, sltly. sol. in xyl. and water.

do 88.8 -phenyl,2- 41 250 69 4 Yel. solid, sol. in methyl 1,2- wtr. antlhot propanedimethanol Sltly. amine. sol. in benzene.

6c Potassium 92.8 N,N-diethyl 29 250 68 4 Pole white solid,

epoxy ethylene sol. in'wtr. and stearate. diamine. hot methanol, in-

501. in benz.

7c do 92.8 Ethylene di- 17.7 250 3 White solid. Sol.ln

amine 85% wtr. and hot;

methanol, insol. in benzene.

8c do 92.8 3,3-iminobls- 32.8 250 70 3 Yel. solid sol. in propylawtr.and-hot v mine. methanol, insol.

in benzene and cold methanol do 92. 8 3,3-iminobis- 16. 4 250 71 3 Yelwhite soft propylasolid sol. in isomine. propanol, sltly. sol. inbenzene and water. 10c do.-..-.. 92.8 Hydrazlne 12.5 250 69 3 Whitesolid sol, ln

monohywtr. and hot drate. methanol, insol.

in benzene and isopropanol.

13" PART 4 As has been previously suggested, having obtained aderivative of an epoxidized ester, for instance, an epoxidized glycerideor ester of a monohydric alcohol, the prept In a one-liter beaker, 9-1.5grams'of the o 14?? any otherconventional procedure. This is illustratedby Examples 'le through 12a in Table 7, following.

Example 1e 7 i reaction prodaration of a sodium salt or the equivalentsalt, such as H the potassium salt or the lithium .saltorthe-like,merely Qbtamed m f l d1ss1ved,m depends on a comparatively simplesaponification reaction grams of Into, ithls 501mm, f 7 which isconducted in the conventional manner, usually calcmm chloride solutionwere added w th vigorous stirin the presence of a solvent, and at atemperature of about soon the chlonde a a whlte dfmse for two or threehours or thereabouts Such 10 precipltate was'formed- Themrxture was.first stirredrz: procedure is illustrated by Examples 1d. through 24d,at room temperature Q -9... for .1 9??? t i fil which appear in Table 6following was warmed at 50 C. foran hour to allow the PICClPlrate tosettle. After settling, the precipitate was washed Example 4 V v, I r bydecantation,*filtered ina'flutedfilter and, dried under 150 grams ofepoxybutyl stearate and 13.7 grams of 15 vacuum. The driedproduct was awhite solid, soluble hydrazine were reacted at 110 C. tor 3 hours(Example in hot benzene and a benzene, isopropanol mixture, in- 2a). To141 grams of this reaction product, 117 grams soluble in water. of 12%sodium hydroxide were added, ,This heterogeneous PART 6 mixture wasreacted at 98 C. under slight reflux until a clear homogeneous solutionwasformed. Then it was The products herein described fall into twoclasses, heated for another hour to insure complete reaction. The one inwhich Salts are Wale! l #9 install? h total time of reaction was 2hours. The-pr duct, 50% 1 sodium salts, potassium salts, lithium salts,or the like, in concentration, was a clear yellow gel. The dried prodandthe other where the salts are Water insoluble, such not was ayellowishwhite powder, soluble in hot methanol, as the calcium salt, magnesiumsalt, barium, aluminum, insoluble in xylene, petroleum ether anddioxane. Its Zinc, and iron salts. The water soluble salts may be'usedwater solution is surface active. f p for the resolution of petroleumemulsions of the water- TAB 6 Compd. Amt., Alkali Amt, Solvent Temp.,Time, Product of Ex. No. Used gms. Used gms. vg r, 0. hrs. Reaction 1a2a 141 Sodium Hy- V 14 Y 103 as 2 soln. yellow droxide. eoloredgel. Alsosol. in hot methanol. InsoLinxylene or petroleum ether. 9 441 165 d 14 p127 98 2 Do. 3a 6a 195 .do. 14 157 -98 2 Do. 14 122 as 2 Do. 14 128 9a 2Do. 14 210 98 2 Do. 14 207 -98 2 Do. 18 15s 98 2 Do. is 157 98 2 Do. 1a171 9s 7 2 Do. 24 131 I as V 2 Do.

11.2 13a 98 2 Do; 22.4 12s 98 2 D0. 11.2 130 98 2 11.6 114 98 2.5 50%soln. yellow a colored gel.

Dried product is yellowish to white solid, so]. in hot methanol, lnsol.lnbenzene or petroleum ether. 120 do 10. 6 114 98 2. 5 D0. 120 do 16. 6120 98 2. 5 Do. 120 dn 12 p 115 98 2.5 D0, 120 -do.- 11.1 114 98 2.5 Do.120 Potassium 17.8 120 98 2.6 Do.

hydroxide 120 do..... 16.7 120 98 2.5 Do. 100 (in 8.9 104 98 2.5 D0. 100do 9.75 v 104 98 2.5 Do. 100 ..-do 8 104 98 2.5 Do.

PART 5 p in-oil type. The water insoluble salts in many instances..Having obtained a suitable water soluble salt Pap are particularlyvaluable as additives for lubricating oils ticularly a sodium orpotassium salt of the kind illus- Whlch are m w l' f otherthanvpetmlgum' trated by Examples 112 through ?Ad in Table 6, preced-The F FF l' d w h g water o l ing, obviously all that is required toconvert such a salt or not, J so long ey lfeasonably l d li into thecalcium, magnesium or other comparable water rs q and P 3 4 P oinsoluble salt, is to follow the same procedure employed dlhmons, fi Y bas .fuel O11 addmves thegmanf for the preparation of zinc oleate, coppernaphthenate, 116T descrlbed Patent 2,553,183 dated May magnesium'stearate, etc. 1951, to Caron et al. They can be used in substantiallyBriefly stated, this simply means reacting the two appropriate reactantsin stoichiometric ratios, washing so as to remove the water solublesalts formed as, for example, sodium chloride, potassium chloride or thelike, and subthe same proportions or lower proportions and this isparticularly true when used in conjunction with a glyoxalidine or amidoglyoxalidine.

I An analogous use in which these products are equally jecti ng thewashed precipitate to drying, if required, or satisfactory, is thatdescribed in US. Patent 1Io. 2,65,-

TABLE 7 Ex Compd. Salt used Amt., No. Used gms.

Amt, gms.

Water, gins Temp., C.

Time,

Product of Reachrs. tion Calcium chloride Barium chloride.

6t BIZ-50%.-- 153 d0.

Aluminum chloride.

8e 12d50% .----do 13. 3 400 9c Mil-50%.- 137 10a. Hid-50%-. 185 .....(1024 400 White solid, sol. in hot benzene and benzeneisopropanol mix,iusol. in water.

Yel. white solid,

sltly. 501. in xyl. and isopropanol. Sol. in hot alcohol or xyleneisopropanol mix. insol. in water.

Yel. soft solid sltly. sol. in xyl. Sol. in xyl. lsopropanol mix.

Pale yel. solid.

0. 5 Sltly. sol. in xyl. Sol. in hot xyl. or xyl. and isopropanol mix.

Yel. white soft 0. 5 solid fairly so].

in xyl. and isopropanol. Insol. in water.

White soft solid.

fairly sol. in xyl. and isopropanol.

White solid. SoLin benzene, sltly. sol. in isopropanel. Lnsol. inpetroleum ether.

8 Green vise. liq.

Cools into soft solid. Fairly sol.

in benzene.

Sltly. sol. in

isopropanol. 2 White solid.

0. 5 Fairly sol. in

benzene, insol.

in isopropanol.

P MN (JIM 978, dated January 12, 1954, to Stayner et al.- The amountemployed is in the same proportion or' lesser amounts than referred toin said aforementioned Caron et al. patent.

The second use is for the purpose of inhibiting fogs in hydrocarbonproducts as described in US. Patents Nos. 2,550,981 and 2,550,982, bothdated May 1, 1951, and both to Eberz. Here again it can be used in thesame proportions as herein indicated or even smaller proportions.

A third use is to replace oil soluble petroleum sulfonates, so-calledmahogany soaps, in the preparation of certain emulsions, or soluble oilsor emulsifiable lubricants where such mahogany soaps are employed. Theproducts serve to replace all or a substantial part of the mahoganysoap.

Another use is Where the product do% not serve as an emulsifying agentalone but serves as an adjunct.

Briefly stated, the fourth use is concerned with use as a coupling agentto be employed with an emulsifying agent. See The Composition andStructure of Tech nical Emulsions, J. H. Goodey, Roy. Australian Chem.Inst. J. and Proc., vol. 16, 1949, pp. 47-75. As stated in the summaryof this article The technical oil-inw'ater emulsion is regarded as asystem of four components: the dispersion medium, consisting of thehighly polar substance water; the disperse phase composed ofhydrocarbons or other substances of comparatively weak polarity; thecoupling agent, being an oil-soluble substance involving an hydroxyl,carboxyl or similar polar group; and the emulsifying agent, which is awater-soluble substance involving an hydrocarbon radical attached to airionizable group.

Fifth, these materials have particular utility iriincreasing the yieldof an oil well by various procedures" which in essence involvefracturing of the strata by I,

crevices, openings or the like.

Such compounds or derivatives also are effective. for

other purposes, such as an anti-fogging agent-in motor fuels, acoagulation preventivein burner oils,- and as an additive for theprevention of corrosion of ferrous metals. Such invention, however, isnot part of what .is. herein.

claimed.

The herein described products and the derivatives thereof areparticularly valuable in flooding processes for recovery of oil fromsubterranean oil-bearing strata when employed in the manner described:in US. Patent 'No;.- 2,233,381, dated February 25.1941, to DeGrobte-and Keiser.

Furthermore, the herein described products may be employed to increaseoperating efficiency by increasing the oil-to-brine ratio or byincreasing the'total 'oilrecovcry in primary recovery operations asdifferentiated from secondary recovery operations. The proceduresemployed are essentially those as described in either-US. Patent No.2,331,594, dated Octo'ber 12, 1943,16 Blair', o'r'-U.'St Patent No.2,465,237 dated March 22, 1949, to Larsen.

When the products of the kind herein described are used for waterflooding and particularly in the form of salts, they have unusual valuein a fresh water or brine system for the inhibition of the growth ofboth anaerobic and aerobic bacteria but are particularly applicable. incontrolling the sulfate reducing organisms which cause difiiculty insecondary recovery operations. Thus, one may use some other agent .oragents in waters-flood systems and use compounds as herein describedprimarily for reducing bacterial growth. The use of such industrialbactericide is well known and the procedure is conventional; forinstance, one can use the methods described in an article entitled TheRole of Microorganisms by R. C. Allred, which appeared in ProducersMonthly, vol. 18, No. 4, pages 18-22.

The products herein described are particularly valuable as industrialbactericides and this applies to both the water soluble salts andparticularly those which are water soluble even when converted into thecopper salt. The copper salts, even if water insoluble, when mixed withsuitable dispersing agents, for instance, the analogous sodium salts,are unusually effective as bactericides.

Previous reference was made to the fact that the herein describedproducts, even after the carboxyl group has been converted at least inpart, or entirely, into a salt form, still may have basic amino groupspresent which in turn may combine with acids such as glycolic acid,oleic acid, naphthenic acid, gluconic acid, petroleum sulfonic acid ofeither the green acid type or the mahogany acid type, or the like andconsiderably change the solubility in either water or oil or othervehicles and thus make these forms suitable for practically any or allpurposes previously mentioned and this applies particularly to the useof additives in fuel oils or the like. Indeed, such combinations areparticularly useful in the resolution of petroleum emulsions of thewater-in-oil type.

It is understood in the hereto appended claims that reference to thecompounds includes such variants obtained by neutralization of residualbasic amino groups with one or more of the acids previously noted, i.e.,either acids are introduced and give predominantly hydrophobe effect ora predominantly hydrophile effect.

As is obvious, if epoxidized compounds of the kind herein described, forinstance, epoxidized soybean oil or, more conveniently, epoxidizedbutylsoyate, are reacted with a polyamine such as ethylene diamine,diethylene triamine, triethylene tetramine, tetraethylene pentamine, thederivatives so obtained can be saponified and acidified underappropriate conditions so it is possible to obtain an inner or an intrasalt involving a basic amino radical and a residual carboxyl radical.

However, if such product, or a suitable intermediate, or the initialproduct itself, is saponified with a strong base, such as caustic sodaor caustic potash, or the like, the resultant product is characterizedby the presence of a metallic ion, for instance, sodium or potassium, inthe carboxyl portion and the amino group is merely part of the acylradical. Both types of products can be obtained by conventional meansfrom the herein described resultants, i.e., either the so-called freeacid which in esscnce really is an inner salt or an intra salt, or thesalt formed by the use of sodium hydroxide, potassium hydroxide, or thelike. The products so obtained whether metallic salts or inner salts orintro salts are effective for the prevention of corrosion, not only inan aerobic system but also in an anaerobic system.

Having thus described our invention what we claim as new and desire toobtain by Letters Patent, is:

l. A member selected from the class of salts and acid salts of thestructure said salts and acid salts being derived from saponifiablepolyamine reacted acyl radical containing epoxidized compounds whereinthe fatty acid radical prior to epoxidation is and in which R and R arethe conventional hydrocarbon radicals of unsaturated fatty acidscomposed only of carbon, hydrogen and oxygen atoms having not over 22carbon atoms and each containing at least 3 carbon atoms; in which R isthe radical of a polyamine composed only of carbon, hydrogen, nitrogen,and oxygen atoms, having up to 20 carbon atoms, and having at least onebasic nitrogen atom, said radical being formed by the removal of ahydrogen atom from an amino nitrogen atom of the polyamine duringrupture of the oxirane ring and linkage of the amino nitrogen atoms witha carbon atom of the oxirane ring, and R is the radical of a polyaminecomposed only of carbon, hydrogen, nitrogen and oxygen atoms, havingnotover 20 carbon atoms and having at least one basic nitrogen atom,said radical being formed by the removal of one hydrogen atom from eachof two separate amino nitrogen atoms of the polyamine during rupture ofthe oxirane rings and linkage of the amino nitrogen atoms with thecarbon atoms of the oxirane rings; and n is a whole number not over 3;and in which Z is selected from the group consisting of group Ia, lb,Ila, IIb and IIIa metal ions, and the cation is selected from the groupconsisting of Z, hydrogen, and lower alkanol radicals and must includeat least one equivalent of Z per anion.

2. A member selected from the class of salts of the structure BIG-OH[CHa-Rr[ (ll ]R2COO] [Z] H --R u said salts being derived fromsaponifiable polyamine reacted acyl radical containing epoxidizedcompounds wherein the fatty acid acyl radical prior to epoxidation is inwhich R, and R are the conventional hydrocarbon radicals of unsaturatedfatty acids composed only of carbon, hydrogen and oxygen atoms havingnot over 22 carbon atoms and each containing at least 3 carbon atoms; inwhich R is the radical of a polyamine composed only of carbon, hydrogen,nitrogen, and oxygen atoms, having up to 20 carbon atoms, and having atleast one basic nitrogen atom, said radical being formed by the removalof a hydrogen atom from an amino nitrogen atom of the polyamine duringrupture of the oxirane ring and linkage of the amino nitrogen atom witha carbon atom of the oxirane ring; in which n is a whole number not over3; and in which Z is selected from the group consisting of group Ia, Ib,Ila, IIb and IIIa metal ions.

3. Salts of claim 2 wherein the radical R is a polyalkylene polyamineradical having a plurality of basic nitrogen atoms.

4. Salts of claim radical, the cation is sodium, is derived from soybeanoil.

5. Salts of claim 2 wherein R-is a diethylene triamine 2 wherein R is anethylene diarnine and the fatty acid radical radical, the cation issodium, and the fatty acid radical Referencesflitediinlthe file nit-bispatent: is derived from soybean oil. a ,a a i i i 6. Salts of claim 2wherein R is a triethylene tetra- UNITED STATES PATENTS amine radical,the cation is sodium; and the fatty acid 2,445,392; Suzi/em e1: a1.; L.'luly 27!,1948 radical is derived from soybean oil. 5 2,645,405?Hughes;i -(Jul'y 21,1953

7. Salts of claim 2 wherein R is a tetraethylene pen- 2,682,5141 Neweylune 29-; 1954 tamine radical, the cation is sodium, and the fatty acid2,712,535 Fisch July 5, 1955 radical is derived from soybean oil.2,761,870 Payne. et a l; Sept. 4; 1956

1. A MEMBER SELECTED FROM THE CLASS OF SALTS AND ACID SALTS OF THESTRUCTURE